Metal-free dental filling system as a substitute for amalgam

ABSTRACT

A metal free dental filling system is provided which prevents the transmission of destructive forces from the shrinking filling material to the sealed dental hard tissue. The system prevents the transmission of destructive forces by making the bond of the cured adhesive sealant to the dental hard tissue, i.e., the enamel, dentin, and root cement, substantially stronger than the bond of the cured adhesive sealant to the filling material. An intermediate layer material may be arranged between the dental filling material and the cured adhesive sealant. If an intermediate layer is used, the bond between the dental hard tissue and the cured adhesive sealant is much stronger than the bond between the cured adhesive sealant and the intermediate layer in order to ensure that substantially no destructive forces are transmitted from the shrinking filing material to the cured adhesive material on the dental hard tissue. The intermediate layer may be removed prior to application of the filling material.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims the priority of the German patent application197 50 319.5, filed on Nov. 13, 1997, and U.S. provisional applicationNo. 60/066,128 filed on Nov. 21, 1997, the disclosure of saidapplications is incorporated herein by reference in its entirety.

TECHNICAL FIELD

The present invention relates to a metal-free dental filling system forfilling therapy or root filling therapy, respectively, as well as to itsuse as a substitute for amalgam.

BACKGROUND ART

For tooth restoration in dentistry, three hierarchically ordered goalsare pursued, whereby each higher standard is based on the fulfillment ofthe lower standard or the lower standards.

The partial goal of the lowest standard 1 consists in the conservationof the dental hard tissue and the protection of the pulpa.

Standard 2 is further aiming at restoring the tooth's shape andfunction.

The purpose of standard 3 is to design the restoration in such a waythat it is imperceptible at conversation distance and remain sothroughout the stipulated service life.

Amalgams, i.e. mixtures of a silver-tin alloy with liquid mercury, havebeen used for more than 150 years as standard filling material, inparticular for posterior, permanent teeth. When used with adequateoperative techniques, amalgam restorations are able to protect thedental hard tissue for years and to restore the tooth's shape as wellit's functionality. Thus, amalgam restorations fully satisfy standard 2.In filling therapy with amalgam, a comparatively simple operativetechnique has evolved that relies on steel matrices and wooden wedgesfor giving the filling its correct, preferably overhang-free contour atits outer surfaces. Occlusal shaping is carried out by carving. Amalgamfillings are furthermore comparatively cheap. The medium survival rateof amalgam fillings can be 10 years and more.

In recent years, however, amalgams have lost quite some ground as astandard restorative material. The main reasons of this decline are,among others, its controversial toxic and allergenic potential, itsenvironmental impact and its lack of tooth color. As a consequence, itwas necessary to search for materials or material systems that could beused to replace amalgam for posterior teeth, in particular for permanentteeth and stress-bearing restorations. This resulted in two material orsystem groups differing in their purpose, namely amalgam alternativesand amalgam substitutes.

Amalgam alternatives have to suffice standard 3 and not only have toguarantee the conservation of the dental hard tissue as well as shapeand function of the restored tooth over a long time, but they also mustbe and remain imperceptible at normal conversation distance. This groupof materials in particular comprises composite fillings and composite orceramic work-pieces. This not only requires tooth color, but also astress resistant, perfect marginal adaptation. With fillings, the latteris achieved by using a rather complex operative technique, withwork-pieces by high accuracy in conjunction with efficient adhesive orcombined adhesive/luting systems.

In contrast to this, an amalgam substitute has to satisfy standard 2just as amalgam does; in addition to this, the operative techniqueshould be simple for cost reasons and be as close as possible to theknown amalgam technique, i.e. it should be possible to work with steelmatrices and wooden wedges, to use a simple incremental technique and,if light curing materials are used, irradiation from an occlusaldirection should suffice.

Various amalgam substitute systems are known:

DE-196 03 577 A1 relates to an adhesive system, wherein a gap freeconnection between the plastic filling material and the dental hardtissue is aimed at. In such a system, the bond between dental hardtissue and filling material is excellent, such that in case of adhesivefailures, continuity fractures occur in the dental hard tissue or in therestorative material. This means that no caries protection is providedalong these marginal openings if they run in the dental hard tissue.

DE 195 44 670 describes an adhesive system that does not harden byradical polymerization but rather as a product of condensation. In thisway, an oxygen-inhibited surface layer is to be avoided. Thus, however,the adhesive may be better suited than usual, radically polymerizingsealants for sealing caries. In the application as an adhesive, where,according to the inventor, the prevention of margin gap formation isagain aimed at, cohesive failure results in the dentin and in theenamel. Hence, this system is unable to reliably protect the dental hardtissue. With comparatively frequent adhesive failure, the enamel is notprotected at all in the area of the marginal openings, which aretherefore not desired at all. In dentin, a partial, erratic,unpredictable protection is to be expected where the bond happens tobreak between the adhesive and the filling material and adhesive islandsremain on the dental hard tissue. The described system thereforeprovides no safe and complete protection of the enamel or dentin, and italso belongs to the category of the adhesive systems aiming at a totalbond between the dental hard tissue and the restorative material.

EP 0 423 430 describes a dentin-adhesive system using a primer and abond on dentin. Again, it is aimed at a total leakage-free bond betweendental hard tissue and restorative material.

EP 0 088 527 describes an enamel conditioner designed to generate abetter bond between the enamel and the restorative material than it usedto be the case upon the usual etching process by means of phosphoricacid.

DE 34 14 163 relates on a dentin primer and describes a dentin bondingsystem working with a primer and a bond on dentin, wherein again a totalleakage-free bond between dental hard tissue and restorative material isdesired.

None of the adhesive systems according to the state of the art, however,uses enamel and dentin bonding selectively for protection and adhesivesealing of the dental hard tissue, while selectively eliminating therequirement of a bond between the shrinking restorative material and thesealed dental hard tissue.

The adhesive systems according to the state of the art are fullyunsatisfactory when being used in combination with amalgam substitutesand the corresponding operative techniques, because unpredictablylocated fractures in the restorative material, the interface betweenrestorative material and adhesive, within the adhesive, at the interfacebetween the adhesive and the dental hard tissue and/or within the dentalhard tissue can occur. Fractures at the interface between the adhesiveand the dental hard tissue and within the dental hard tissue areparticularly damaging. A reliable protection cannot be achieved usingthe required simple placement techniques and currently availableadhesive systems.

Investigations have shown that fillings made of materials presently usedas amalgam substitutes are visible after a short period of timeespecially when occlusally loaded. Such materials include amalgamsubstitutes in combination with an adhesive system such ascomposite-adhesive or compomer adhesive systems, i.e., polyacid-modifiedcomposites, as well as composite adhesive systems specifically developedas amalgam substitutes. Sometimes within months, from 60% to 95% of thetotal margin length of the filling is visible resulting in both marginaldiscoloration and a high risk for secondary caries in medium time rangecaries diagnostics.

While marginal discoloration may be acceptable within the requirementsof operative standard 2, the high risk for secondary caries withfillings of the known material combinations mentioned above, cannotsatisfy operative standard 1, i.e., tooth conservation can not beachieved over a medium time range. Thus, materials presently used asamalgam substitutes should only be used as temporary fillings.

The reason for the failure of the amalgam substitute materials accordingto the state of the art lies in the fact that such materials usuallyshrink by 2.5 to 4.5 volume percent during the curing process. Theresulting stress build-up damages the bonds as generated by the adhesivesystems according to the state of the art and exceeds the cohesivestrength of the dental hard tissue, especially in the enamel, and of thefilling material itself. Under stress, non-predictable continuityfractures occur, namely fissures in the enamel and, more rarely, in thedentin, a breaking of the bond between dental hard tissue and adhesivesystem, within the adhesive system, at the interface between adhesivesystem and filling, and within the filling. Even though an adhesivesystem is used, unprotected, adhesive free areas of dental hard tissueare exposed, either due to cohesive fractures within the dental hardtissue or due to a breaking of the bond between the adhesive system andthe dental hard tissue.

DISCLOSURE OF THE INVENTION

Hence, it is a general object of the invention to provide a dentalfilling system that avoids at least part of the above disadvantages andproblems.

In particular, it was an aim of the present invention to provide anamalgam substitute, which fulfills the above partial goals 1 and 2 aswell as, possibly, 3.

This object is achieved according to claim 1. Preferred embodiments aredescribed in the dependent claims.

The metal free, dental filling system for the filling therapy ofcavities or for the filling therapy of root canals according to thepresent invention comprises

a) a dental filling material for cavities or root canals, as well as

b) an adhesive, curing or self-curing sealant for the dental hardtissue,

c) wherein the adhesive bond of the cured adhesive sealant to the dentalhard tissue, i.e., the enamel dentin, and root cement, is substantiallystronger than to the cured filling material such that substantially nodestructive forces are transmitted from the shrinking filling materialto the adhesive sealant.

In an especially preferred embodiment the filling system according tothe invention comprises an intermediate layer material d), which issuitable to be arranged between the dental filling material a) and thesealant b), wherein the adhesive bond between the cured adhesive sealantb) to the dental hard tissue is much stronger than to the intermediatelayer material d), such that substantially no destructive forces aretransmitted from the shrinking filling material to the adhesive sealant.

Preferably, said intermediate layer material d) is removable beforeapplication of the filling material.

In an especially preferred embodiment, substantially no adhesive bond isformed between the cured sealant b) to the filling material a) or, ifapplicable, to the intermediate layer d), respectively, such that duringthe curing no destructive forces at all are transmitted from theshrinking filling material a) and/or the intermediate layer material d)to the adhesive sealant b).

Hence, in contrast to the known state of the art the present inventiondoes not aim at protecting the dental hard tissue by a perfect bond tothe filling material. The present invention rather provides anisolating, selective adhesive seal of the dental hard tissue, therebygenerating the desired protection in the area of the margin gaps.

Preferably, the desired separation or, compared to the destructivestress build-up within the filling, the weak, no stress transferringbonds between the sealant and the filling material are achieved bymaking known adhesive coatings unable to co-polymerize or lock by asuitable choice of monomers, admixtures or curing methods.Alternatively, instead of using a known adhesive system, an adhesivesystem is used that adheres to the enamel and dentin, forms a coating,is chemically and physically resistant but does not form a mechanical orchemical bond to the filling system that might endanger its own bond tothe hard dental material.

Using the system according to the invention, the dental hard tissueremains free of fractures and is protected against caries and erosiveprocesses throughout the stipulated service life of the filling. Theamalgam substitute according to the invention therefore meets standard 2by a complete prevention of the risk of secondary caries and bypreserving the dental hard tissue, while shape and function of the toothare restored by the filling material.

MODES FOR CARRYING OUT THE INVENTION

The main object of the present invention is a dental filling system thatthat eliminates the need for a total bond from the sealant b) for thedental hard tissue to the filling material a) or the intermediate layermaterial d), respectively. An isolated, selective adhesive sealing ofthe dental hard tissue can be reached as follows:

A) A transmission of shrinking-forces can be avoided by preventingmechanical interlocking and homo or co-polymerization between the dentalfilling material a) and, if present, the intermediate layer material d)on the one hand, as well as the adhesive sealant b) for the dental hardtissue on the other hand. This can e.g. be achieved by entirely coatingthe sealant b) by a separation layer. For this purpose, paintingmaterials, such as zinc oxide-Eugenol, said compound being known tothose skilled in the art, barrier materials, such as powders or powdercoatings, or glycerolacetate-based isolating gels, or primers, e.g.,silicon-organic compounds.

B) The undesired transmission of the shrinking forces from the fillingmaterial to the adhesive sealant can be further prevented by a reductionof the free radicals at the surface of the radically polymerizingsealant. In a further preferred embodiment, the undesired transmissionof the shrinking-forces is therefore prevented by the fact the hardenedadhesive sealant b) has a low free radical content and is therefore notapt for co-polymerization.

It is especially preferred that the hardened sealant b) is even unableto undergo homo- and/or co-polymerization. The ability forco-polymerization of the components a), b) and d) can e.g. be affectedand weakened by admixing of BisGMA(2,2-Bis[4-(2-hydroxy-3-methacryloxypropoxy)phenyl] propane) bicarbonate(of the Bayer Company) or photo-initiators in higher concentrations, orby coating the sealant b) with an arbitrary air blocker as known to theperson skilled in the art before light curing for preventing thebuild-up of an oxygen-inhibited surface layer.

On the other hand, a reduction of the free radicals at the surface of aradically polymerizing sealant can also be reached by a suitable choiceof the monomer systems.

C) In a further preferred embodiment a transmission of shrinking-forcesis reduced or diminished by using filling materials d) and adhesivesealants b) of different polarity, notably for suppressing wetting. Itis especially preferred to use a hydrophilic or amphiphilic sealant forthe dental hard tissue and a strongly hydrophobic filling system.Particularly preferred is thereby a sealant b) being hydrophilic oramphiphilic, whereby the filling material a) is strongly hydrophobic,e.g., Etch & Prime 3.0 or Prime & Bond NT (of the Dentsply company)combined with Adaptic II (Johnson & Johnson) or Pertac (Espe company).Also preferred is a sealant b) being hydrophobic whereas the fillingmaterial is strongly hydrophilic, e.g. Visiobond (Espe company) incombination with PhotacFil (Espe company) or Ketac (Espe company) Bond.

D) Especially, if the dental filling material a) is a methacrylatedsubstance, the adhesive sealant b) has a separating effect in respect tothe filling material a) due to a different polymerization that does notallow a co- or homo-polymerisation of di- or polyacrylatesystems. Thisprevents a shrinking-force transmitting bond between the adhesivesealant and the filling material. Preferred sealants for the dental hardtissue are selected from the group comprising water glass, silica esterhydrolysates, polymerizable silane compounds, natural resin varnishes,cyanate based varnishes, epoxide resins, epoxidated soy oil orepoxy-modified silicones. They can preferably be selected as follows:

water glass: e.g. a water glass glue in colloidal solution of potassiumor sodium silicate, wherein the setting takes place, e.g. throughevaporation of the water share.

silica ester hydrolysates: Through the preparation of partialhydrolysates of silica ester hydrolysates, solid resin coatings can beachieved. The mode of preparation of such a coating could be e.g.vinyltriethoxysilane 12% per weight, silica ester TES (tetraethoxysilane) (Dynamit Nobel) 34% per weight, phosphoric acid 0.3% per weightdissolved in acetone. After the evaporation of the solvent, clear, hard,shining hydrophobic films are formed. The adhesion to substrates such asdentin and enamel can be adjusted by means of metal acetylacetonates.

polymerizable silane compounds: preferably silanes being modified withepoxide- or methacrylate groups. The mentioned reactive silane monomerscould contain metal complexes having an affinity to the dentin or theenamel, e.g. compounds with calcium, fluorine or other halides;

epoxy resins: As an example the epoxide-modified vinylester resins,polyester resins, vinyletherresins or bisphenol-A-epoxid resin (DowCorning) Dercane Oligomer; vectomer-vinylether oligomeres,ISP=vinylether (ISP company), CIBA Araldit types (Ciba-Geigy company);Union Carbide cycloaliphatic epoxides are to be mentioned. Depending ontheir modification, said raw materials could be polymerized throughradical or ionic initiation, thus providing 2-component systemshardening chemically, e.g. following to the preparation comprising thecomponent A: bisphenol-A-epoxy resins (D.E.R. 335 Dow Corning); Cumenehydroperoxide and component B: bisphenol-A-epoxyresin, silane Z-6020(Dow Corning) and triethanolamine. Correspondingly the formulations thatharden upon light exposure are conceivable with light in the visible orultra-violet range, e.g. following to the preparation Vectomer 2010urthan oligomer (of the Vectomer company) 45% per weight, monomer 401015% per weight, Rapicure CHVE (of the ISP company) monomer 39% by weight(1,4-cyclohexane-dimethanole-divinylether), cationic initiator UVI-69741% per weight.

natural resin varnishes: Through hydrophobic natural resin varnishesforming films, dense, hydrophobic coatings could be achieved, e.g.following the preparation of Cophonium 12% per weight, Shellac 25% perweight, gum arabic 8% per weight, Cellulose 5% per weight and AlkoholDAB (Deutsches Arzneibuch) to make 100%.

epoxidated soy oils: They are cross-linkable through cationic or radicalinitiation, e.g. Henkel Edenol types; further examples for reactiveoligomers are cyracure oligomeres (Union Carbide), cycloaliphaticepoxide resins like UVR 61110 (Dow Corning), i.e.3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane-carboxylate, or UVR 6128(Dow Corning), i.e. bis-(3,4 epoxycyclohexyl-adipate or UVR 6216 (DowCorning), i.e. 1,2-epoxyhexadecane.

methacrylic or epoxy-modified silicones (e.g. of Goldschmidt, Wacker,Mitsubishi) as well as methacryl-modified gelatines and cellulose estersalso display good film forming properties: they could also serve asfilm-forming carrier materials for a variety of active agent, likefluorides or antiseptic or bactericidal additives. The desiredseparation effect is notably achieved by employing 2 different synthesisforms. Said process could be achieved through different cross-linkagemechanisms, like the chemical hardening, the light-induced hardening,the radical- or cationic induced hardening, cross-linking throughradical condensation etc.

The filling materials a) comprise plastics, composites, compomers,ormaceres, ceromers, polyglasses, glass ionomer cements, carboxylatecement, phosphate cement, EBA (ethoxybenzoic acid) cement (ESPE company)or guttapercha, or materials consisting thereof. These materials arepreferably photo curing, chemically curing, dually curing, heat curingor thermoplastic.

The above mentioned compounds are commercially available and aregenerally known by persons skilled in the art.

The sealants b) for the dental hard tissue exhibit a good bond with thedental hard tissues. They form a leakage-free and gap-free, closed,mechanically and chemically resistive protective layer and, if possible,release (as a “smart material”) caries protective agents, i.e. theyrelease plaque-suppressing or caries-protective agents permanently orupon request, such as fluorides, chlorhexidine, triclosan, calcium orhydoxyl-ions. Preferably used sealants for the dental hard tissue arephoto hardening, chemically hardening, dually curing, heat curing orthermoplastic or they cure using the principles of contact glues.

In a highly preferred embodiment the dental filling material a) is photohardening (i.e. hardening upon exposure to light of a suitablewave-length) and the sealant b) for the dental hard tissue is chemicallyhardening.

In another preferred embodiment the dental filling material a) ischemically curing and the sealant b) for dental hard tissue is photocuring.

The adhesive sealant b) can further also be used as a base material, asa proximal sealant or as a fissure sealant.

Using the filling system presented here, it is possible to preparefillings that are metal free and preferably tooth colored with arequired simple, economical operative technique corresponding to thegeneral skill of the dentist. Such filling systems are true amalgamsubstitutes because they not only restore the tooth's shape and functionbut also protect the same against caries and erosion. Analogously, suchsystems can also be used for root fillings.

A further aspect of the present invention is a method for fillingtherapy of cavities or root canals by using one of the dental fillingsystems described above.

The present invention shall, in the following be illustrated by thefollowing examples, which are not to be construed as limiting the scopeof the invention.

EXAMPLE 1

The following sealants are set forth for the purpose of the ensuingcreation of a filling system:

a) sealing through radical crosslinking: BisGMA or 49.0% per weightUrethane DMA (dimethacrylate) hydroxyfunctionalized 29.5% per weightmethacrylate acid modified 20.0% per weight polymethacrylatephotoinitiator system 1.5% per weight b) sealing through low-shrinkingcationic cross-linking epoxy functionalized 70% per weight oligomerepoxy functionalized 27% per weight polyol cationic initiator 3% perweight c) low shrinking composite by cationic cross- linking: epoxyfunctionalized 25% per weight resin mixture x-ray active Ba/Al- 75% perweight borosilicate glass <2.0 micron

EXAMPLE 2

A cavity is sealed upon using the composition a) of example 1, andthereafter it is filled with the low-shrinking composite c) of example 1and is finally irradiated with a polymerisation lamp for about 60seconds. The filling thus obtained does not form any bond with thesealant having been formed upon radical cross-linking and formstherefore a dense, strainable and durable filling system due to theminimal shrinkage. There is essentially no tension transfer to thedental hard tissue.

EXAMPLE 3

Cavities, tiny lesions or fissures are sealed and cured (hardened) witha radically cross-linking sealant according to item a) of example 1).Thereafter the sealing resin according to item b) of example is appliedand irradiated for about 60 seconds. The result is a stress-free sealingof said cavity, lesion or fissure. Due to the high conversion rate ofthe cationic cross-linking system of item b) of example 1, aninhibition-free layer is the result. Plaque, beverages like tea, coffeecould not cause any discolorations. The chemical degradation doesintervene only to a minor extent. The mechanical abrasion could also bediminished.

EXAMPLE 4

A cavity is filled with a composite c) of example 1). Due to the highconversion rate of the preceding cationic sealing, no chemical bond isgenerated between the sealant and the filling material. The result is asolid, stress-resistant filling on the one hand and a well-protectedadhesive sealing of the dental hard tissue on the other hand. Due to theabsence of material shrinkage-related stress, the comfort for carryingsuch a restoration is to be underlined.

EXAMPLE 5

Conventional fillings having been placed with commercially availablecomposites or compomers (i.e. acid-modified composites) could also besealed-off by means of a cationic cross-linking sealant according toitem b) of example 1, thus avoiding secondary caries resulting fromshrinkage of the filling material.

While there are shown and described presently preferred embodiments ofthe invention, it is to be distinctly understood that the invention isnot limited thereto but may be otherwise variously embodied andpracticed within the scope of the following claims.

What is claimed is:
 1. A metal free dental filling system for thefilling therapy of cavities or root canals, characterized in that itcomprises: a) a dental filling material for cavities or root canals, andb) an adhesive, curable or self-curing sealant for the dental hardtissue, c) wherein the adhesive bond from the adhesive sealant to thedental hard tissue is stronger than the adhesive bond from the adhesivesealant to the cured filling material, such that substantially nodestructive forces are transmitted from the shrinking filling materialto the adhesive sealant.
 2. The dental filling system of claim 1,wherein it further comprises an intermediate layer material arrangedbetween the dental filling material and the adhesive sealant, whereinthe adhesive bond from the adhesive sealant to the dental hard tissue isstronger than the adhesive bond from the adhesive sealant to theintermediate layer material, such that substantially no destructiveforces are transmitted from the shrinking filling material to theadhesive sealant during curing.
 3. The dental filling system of claim 2,wherein the intermediate layer material is removable before theapplication of the filling material.
 4. The dental filling system ofclaim 1, wherein substantially no adhesive bond is formed between thecured adhesive sealant and the filling material or the adhesive sealantand the intermediate filling material, such that transmission of thedestructive forces from the shrinking filling material or theintermediate layer material to the adhesive sealant during curing isprevented.
 5. The dental filling system of claim 1, wherein the bondsbetween the adhesive sealant and the dental filling material or theadhesive sealant and the intermediate layer material do not show amechanical interlocking or bonding to each other caused by homo- orco-polymerization.
 6. The dental filling system of claim 5, wherein themechanical interlocking or bonding by homo- or co-polymerization isprevented by fully coating the adhesive sealant with a separation layerselected from the group consisting of painted materials, barriermaterials, and glycerol-acetate containing isolating gels or primers. 7.The dental filling system of claim 1, wherein the free radicals at thesurface of the cured adhesive sealant are reduced such that the adhesivesealant is not apt for co- or homo-polymerization with the fillingmaterial or the intermediate layer material.
 8. The dental fillingsystem of claim 7, wherein the cured adhesive sealant is unable toundergo homo- and/or co-polymerization at the common interface surfaceswith the filling material or the intermediate layer material.
 9. Thedental filling system of claim 7, wherein co-polymerization of theadhesive sealant and the filling material or the adhesive sealant andthe intermediate layer material is weakened by an admixture of2,2-bis[4-(2-hydroxy-3-methacryloxypropoxy)phenyl] propane (BisGMA)bicarbonate or an excess of photo-initiators, or by coating the adhesivesealant with an air blocker prior to light-curing for preventing thebuild-up of an oxygen inhibited surface layer.
 10. The dental fillingsystem of claim 1, wherein the filling material, the intermediate layermaterial, and the cured adhesive sealant are differently polar forsuppressing wetting.
 11. The dental filling system of claim 10, whereinthe cured adhesive sealant is hydrophilic or amphiphilic and the fillingmaterial is hydrophobic.
 12. The dental filling system of claim 1,wherein the filling material is a methacrylated substance and theadhesive sealant does not allow co- or homo-polymerization of di- orpolyacrylate systems such that a shrinking-force transmitting bondbetween the sealant and the filling material is prevented.
 13. Thedental filling system of claim 12, wherein the adhesive sealant isselected from the group consisting of water glass, silica esterhydolysates, polymerizable silane compounds, natural resin varnishes,cyanate containing varnishes, epoxy resins, epoxidated soy oils, andepoxy modified silicones.
 14. The dental filling system of claim 1,wherein the dental filling material and/or the sealant are photohardening, chemically hardening, dually hardening, heat hardening,thermoplastic, or, wherein the dental filling and/or the sealant hardenupon contact with a surface containing the same material.
 15. The dentalfilling system of claim 14, wherein the filling material is light curingand the sealant is chemically self-curing.
 16. The dental filling systemof claim 14, wherein the filling material is chemically self-curing andthe sealant is light curing.
 17. The dental filling system of claim 1,wherein the filling material is selected from the group consisting ofplastics, composites, ceromers, polyglasses, glass ionomer cements,carboxylate cement, phosphate cement, ethoxybenzoic acid (EBA) cement,and guttapercha.
 18. The dental filling system of claim 1, wherein theadhesive sealant releases plaque-suppressing or caries-protectiveagents.
 19. The dental filling system of claim 1, wherein the dentalfillings are tooth colored.
 20. A method for therapeutic and restorativetreatment of cavities and for therapeutic and restorative root canalscomprising the acts of filling a cavity or root canal of a patientaccording to the dental filling system of claim
 1. 21. The dentalfilling system of claim 6, wherein said painted materials include zincoxide-Eugenol.
 22. The dental filling system of claim 6, wherein saidbarrier materials include powders or powder coatings.
 23. The dentalfilling system of claim 6, wherein said glycerol-acetate containingisolating gels or primers include silicone-organic compounds.